CN116948515A - Anti-fouling coating liquid composition, preparation method and application - Google Patents

Anti-fouling coating liquid composition, preparation method and application Download PDF

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Publication number
CN116948515A
CN116948515A CN202310921663.6A CN202310921663A CN116948515A CN 116948515 A CN116948515 A CN 116948515A CN 202310921663 A CN202310921663 A CN 202310921663A CN 116948515 A CN116948515 A CN 116948515A
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coating liquid
liquid composition
fouling
modified
disulfide bond
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王同心
何张才
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Suzhou Hongdao New Material Co ltd
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Suzhou Hongdao New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • C09D7/62Additives non-macromolecular inorganic modified by treatment with other compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02Details
    • H01L31/0216Coatings
    • H01L31/02161Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/10Transparent films; Clear coatings; Transparent materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

Abstract

The invention belongs to the technical field of solar photovoltaic backboard, and particularly relates to an anti-fouling coating liquid composition, a preparation method and application. The raw materials of the composition comprise main resin, an anti-fouling filler, a photoinitiator, an organic solvent, a silane coupling agent and an auxiliary agent; wherein the antifouling filler comprises disulfide bond compound modified Al 2 O 3 And hexadecylpolysiloxane modified SiO 2; The mass ratio is 1:5-5:1. The outer surface of the backboard prepared by coating is a self-repairing fluorine-free anti-fouling coating, so that the backboard has long-term self-cleaning performance, and long-term power generation efficiency of the solar cell is ensured.

Description

Anti-fouling coating liquid composition, preparation method and application
Technical Field
The invention belongs to the technical field of solar photovoltaic backboard, and particularly relates to an anti-fouling coating liquid composition, a preparation method and application.
Background
The photovoltaic backboard is used as a packaging material on the back of the photovoltaic module, can resist the erosion of the environment such as light, humidity and heat on materials such as a battery piece, an adhesive film and the like, plays an insulating protection role, and is a key raw material for prolonging the service life of the photovoltaic module.
In recent years, BIPV market shows an expanding trend, and a transparent backboard becomes a new direction under the double requirements of weight reduction and double-sided power generation gain, so that head backboard enterprises enter the field of transparent backboard in a dispute manner. The transparent backboard is made of a fully transparent material, the weight of the transparent backboard is lighter, the installation and maintenance are convenient, and the assembly adopting the transparent backboard has more application scenes compared with the double-glass assembly. Meanwhile, as the back plate is mature in application, the transparent back plate is adopted to realize the production of the double-sided power generation assembly, and the factory building and equipment transformation cost is saved for assembly manufacturers, so that the back plate is favored in the industry.
At present, more and more transparent back plates adopt a coating type structure so as to meet the requirements of reliability and continuous cost reduction, and truly realize sustainable development of the photovoltaic industry. Conventional fluorine films have a very high surface energy, and their surfaces are easier to clean than glass, and dust or dirt can be easily blown away by wind or rain. The problems of insufficient sand falling impact resistance and dust shielding of the coated transparent backboard are gradually highlighted, and the influence on the power generation efficiency and the power generation capacity of the assembly is gradually highlighted.
The Chinese patent application No. CN202210393613.0 discloses a preparation method and application of a transparent long-acting easy-to-clean flame-retardant anti-fouling coating for a photovoltaic panel. By adding the functional resin containing fluorine-silicon into the acrylic resin containing flame-retardant polyurethane, the super-hydrophobicity, high light transmittance, yellowing resistance, extremely high cleaning property and flame retardance of the coating are improved. But cannot improve the sand fall impact resistance of the coated back plate.
Therefore, development of a self-cleaning coating which has superhydrophobicity, high light transmittance, long-acting anti-fouling and high wear resistance at the same time is urgently needed to ensure normal operation of the solar cell.
Disclosure of Invention
In order to overcome the defects, the invention provides an anti-fouling coating liquid composition, a preparation method and application. The outer surface of the backboard prepared by coating is a self-repairing wear-resistant and anti-fouling coating, so that the backboard has long-acting self-cleaning performance, and the implementation impact resistance of the backboard is improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
an anti-fouling coating liquid composition comprises main resin, anti-fouling filler, photoinitiator, organic solvent, silane coupling agent and auxiliary agent; wherein the antifouling filler comprises disulfide bond compound modified Al 2 O 3 And hexadecylpolysiloxane modified SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The disulfide bond-containing compound modified Al 2 O 3 And hexadecylpolysiloxane modified SiO 2 The mass ratio of (2) is 1:5-5:1.
Preferably, the host resin includes a disulfide bond-containing urethane acrylic resin and a silicone-modified urethane acrylate.
Preferably, the mass ratio of the disulfide bond-containing polyurethane acrylic resin to the organosilicon modified polyurethane acrylic ester is 1:3-3:1.
Preferably, the preparation method of the polyurethane acrylic resin containing disulfide bonds comprises the steps of mixing an aromatic polyurethane acrylic acid ester oligomer and 4,4' -diaminodiphenyl disulfide, and reacting for 2-4 hours at 70-90 ℃ in a nitrogen atmosphere.
Preferably, the mass of the 4,4' -diaminodiphenyl disulfide is 1 to 10% of the mass of the aromatic urethane acrylate oligomer.
Preferably, the disulfide bond containing compound modifies Al 2 O 3 The preparation method comprises the steps of reacting 2-hydroxyethyl disulfide with isocyanate methyltrimethoxysilane to prepare a siloxane compound containing disulfide bonds; then Al is added 2 O 3 Adding the disulfide bond-containing siloxane compound and KH550 hydrolysate into the dispersion liquid, and reacting to obtain the final product.
Preferably, the molar ratio of the 2-hydroxyethyl disulfide to the isocyanate methyltrimethoxysilane is 1:1-5.
Preferably, the Al 2 O 3 The preparation method of the dispersion liquid comprises the steps of adding nano Al 2 O 3 Adding into the mixed solution of ethanol and water, and performing ultrasonic dispersion; the mass ratio of the ethanol to the water is 1:1.
Preferably, the reaction is stirred at 70-90 ℃ for 4-8 hours; and after the reaction, centrifuging, separating and drying to obtain the catalyst.
Preferably, the hexadecyl polysiloxane modified SiO 2 The preparation method of (C) comprises the steps of preparing hexadecyltrimethoxysilane, tetraethoxysilane and SiO 2 The catalyst is obtained through HCl catalytic reaction.
Preferably, the reaction is carried out for 20-30 hours at 70-90 ℃ to obtain SiO 2 Modifying the suspension, adding SiO 2 And (3) centrifugally separating the modified suspension, washing with absolute ethyl alcohol, and drying to obtain the modified suspension.
Preferably, the photoinitiator is selected from any one or more of benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, alpha-amine alkyl phenyl ketone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6-trimethyl benzoyl) phenyl phosphine oxide, 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer and 9-phenyl acridine.
Preferably, the organic solvent is one or more of ethanol, n-butanol, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, xylene and butanone.
Preferably, the silane coupling agent is selected from one or more of vinyl trimethoxy silane, vinyl tri (beta-methoxyethoxy) silane, vinyl triisopropoxy silane, vinyl triethoxy silane, gamma-methacryloxypropyl trimethoxy silane and vinyl triacetoxy silane; the auxiliary agent comprises one or two of a leveling agent and a dispersing agent.
Preferably, the auxiliary agent comprises one or two of a leveling agent and a dispersing agent.
Preferably, the raw materials of the composition comprise the following components in percentage by weight:
30% -50% of main resin;
5% -10% of anti-fouling filler;
1% -5% of a photoinitiator;
30% -60% of organic solvent;
1% -5% of a silane coupling agent;
1-8% of auxiliary agent.
Preferably, the anti-fouling coating thickness is 1-5 μm.
Still another object of the present invention is to provide a method for preparing the above coating liquid composition, comprising the steps of: adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the anti-fouling adhesive.
It is also an object of the present invention to provide the use of the above-described coating liquid composition for the preparation of a long-lasting self-cleaning transparent backsheet.
Compared with the prior art, the invention has the following positive and beneficial effects:
(1) The coated transparent backboard of the invention comprises a self-repairable anti-fouling coating, wherein the main resin polyurethane acrylic resin (SAC) of the coating contains disulfide bonds and Al modified by a compound containing the disulfide bonds 2 O 3 After ultraviolet curing and heating, the filler is crosslinked through disulfide bond exchange reaction and double bonds to form a rough surface with a firm micro-nano structure. The anti-fouling coating provided by the invention can be hydrophobic and oleophobic, and has excellent super amphiphobicity and self-repairing performance. By disulfide exchange reaction, al 2 O 3 The filler and SAC form a complete coating again through covalent bonds in the self-repairing process, the damaged coating surface can be repaired again, and the superhydrophobicity is recovered, so that the backboard has a long-acting anti-fouling function.
(2) The antifouling filler of the antifouling coating of the invention is modified Al containing disulfide bond compound 2 O 3 And hexadecylpolysiloxane modified SiO 2 The composition of the (2) obtains a concave-convex micro-nano structure through reasonable particle size control and mass fraction control, so that the coating has excellent hydrophobic and oleophobic performance, ensures the anti-fouling capability of the transparent backboard, maintains the high light transmittance of the backboard, and can also enhance the wear resistance and sand falling resistance of the backboard.
(3) The main resin of the anti-fouling coating is a composition of polyurethane acrylic resin (SAC) containing disulfide bonds and organosilicon modified polyurethane acrylic ester (OSC), and the material characteristics of the two resins can be combined to realize no fluorination of the coating, ensure the weather resistance of the anti-fouling coating, improve the adhesive force of the coating to the weather-resistant coating and improve the wear resistance and impact resistance of the coating.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the present invention, but are merely illustrative of the present invention. The experimental methods used in the following examples are not specifically described, but the experimental methods in which specific conditions are not specified in the examples are generally carried out under conventional conditions, and the materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.
In the following examples and comparative examples of the present invention:
the disulfide bond-containing polyurethane acrylic resin SAC is obtained after being modified by commercial products, and the preparation method is as follows: aromatic urethane acrylate oligomer (Zhan Xin resin, model EBECRYL 204) and chain extender 4,4' -diaminodiphenyl disulfide (5 wt% of oligomer) were added to a urethane prepolymer solution (Ji Ning Duo chemical Co., ltd., model LD 1227) and reacted at 80℃for 3 hours under nitrogen atmosphere to obtain SAC.
Silicone modified urethane acrylate OSC is a commercially available product from a new resin of the skian type EBECRYL8890.
Disulfide bond containing compound modified Al 2 O 3 For self-making, the preparation method is as follows:
(1) Weigh 5g of nano Al 2 O 3 (Jikang, model SS-LY 30) in a 250ml round bottom flask, adding 200ml ethanol and water mixture (ethanol: water=1:1, mass ratio) into the flask, and performing ultrasonic dispersion for 30min to obtain Al 2 O 3 And (3) a dispersion.
(2) The 2-hydroxyethyl disulfide and isocyanate methyltrimethoxysilane are reacted for 2 hours at 80 ℃ according to the mol ratio of 1:2, so as to obtain the siloxane compound containing disulfide bonds. 0.15g of silane coupling agent KH550 was weighed, 4g of deionized water was added, and the pH was adjusted to approximately pH 3 with glacial acetic acid, allowing the silane coupling agent to hydrolyze sufficiently.
(3) To Al 2 O 3 Adding the 0.1g disulfide bond siloxane compound and KH550 hydrolysate into the dispersion, stirring at constant temperature of 80 ℃ for 6 hours, centrifuging after the reaction is finished, washing with absolute ethyl alcohol for 4 times, drying in an oven at 80 ℃ for 24 hours, and grinding for later use.
Hexadecyl polysiloxane modified SiO 2 For self-making, the preparation method is as follows:
(1) Hexadecyltrimethoxysilane (HDTMS), tetraethoxysilane (TEOS) and SiO 2 Particle (Anhuixin Crystal material, high purity spherical SiO) 2 1-3 microns) is prepared by HCl catalysis reaction, and SiO is formed after 24-h reaction at 80 DEG C 2 Modifying the suspension.
(2) Will SiO 2 The modified suspension is centrifugally separated, washed by absolute ethyl alcohol for 4 times, dried in an oven at 80 ℃ for 24 hours and ground for standby.
Example 1
The coating liquid comprises the following components in parts by mass:
a bulk resin (SAC/OSC mass ratio=1:3) 30%;
antifouling filler (disulfide bond compound modified Al) 2 O 3 Hexadecylpolysiloxane modified SiO 2 Mass ratio = 1:5) 5%;
1% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone);
60% of an organic solvent (propylene glycol methyl ether acetate);
1% of a silane coupling agent (vinyl trimethoxy silane);
auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1 (m/m) 3%).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Example 2
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
35% of a main resin (SAC/OSC mass ratio=1:3);
antifouling filler (disulfide bond compound modified Al) 2 O 3 Hexadecylpolysiloxane modified SiO 2 Mass ratio = 1:3) 6%;
2% of a photoinitiator (alpha-aminoalkylphenone);
46% of organic solvent (propylene glycol diethyl ether acetate);
3% of a silane coupling agent (vinyltriethoxysilane);
auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1 (m/m) 8%).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Example 3
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a bulk resin (SAC/OSC mass ratio=1:3) 40%;
antifouling filler (disulfide bond compound modified Al) 2 O 3 Hexadecylpolysiloxane modified SiO 2 Mass ratio = 1:1) 7%;
3% of a photoinitiator (1-hydroxycyclohexyl phenyl ketone);
organic solvent (ethyl acetate) 39%
Silane coupling agent (vinyl triisopropoxysilane) 5%;
auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1 (m/m) 6%).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Example 4
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a bulk resin (SAC/OSC mass ratio=2:3) 45%;
antifouling filler (disulfide bond compound modified Al) 2 O 3 Hexadecylpolysiloxane modified SiO 2 Mass ratio = 3:1) 8%;
4% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone);
37% of organic solvent (propylene glycol methyl ether acetate/butanone=1:1 volume ratio);
2% of a silane coupling agent (vinyltriacetoxysilane);
auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1 (m/m) 4%).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Example 5
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a bulk resin (SAC/OSC mass ratio=1:3) 40%;
antifouling filler (disulfide bond compound modified Al) 2 O 3 Hexadecylpolysiloxane modified SiO 2 Mass ratio = 5:1) 10%;
5% of photoinitiator (9-phenylacridine);
35% of an organic solvent (propylene glycol methyl ether acetate/n-butanol=2:1, volume ratio);
silane coupling agent (vinyltris (. Beta. -methoxyethoxy) silane) 5%;
auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1) 5%.
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Example 6
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a bulk resin (SAC/OSC mass ratio=1:2) 30%;
antifouling filler (disulfide bond compound modified Al) 2 O 3 Hexadecylpolysiloxane modified SiO 2 Mass ratio = 1:5) 5%;
1% of a photoinitiator (1-hydroxycyclohexyl phenyl ketone);
60% of an organic solvent (n-butanol);
1% of a silane coupling agent (vinyltris (. Beta. -methoxyethoxy) silane);
3% of auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Example 7
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a bulk resin (SAC/OSC mass ratio=1:1) 30%;
5% of an antifouling filler (disulfide-bond-containing compound modified Al2O 3/hexadecyl polysiloxane modified SiO2 mass ratio=1:5);
1% of a photoinitiator (2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide);
60% of an organic solvent (propylene glycol diethyl ether acetate);
1% of a silane coupling agent (vinyl trimethoxy silane);
3% of auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Example 8
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a bulk resin (SAC/OSC mass ratio=3:1) 30%;
antifouling filler (disulfide bond compound modified Al) 2 O 3 Hexadecylpolysiloxane modified SiO2 mass ratio = 1:5) 5%;
1% of photoinitiator (2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer);
60% of an organic solvent (propylene glycol diethyl ether acetate);
1% of a silane coupling agent (vinyltriethoxysilane);
3% of auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Comparative example 1
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a bulk resin (SAC/OSC mass ratio=1:3) 30%;
anti-fouling filler (hexadecyl polysiloxane modified SiO) 2 )5%;
1% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone);
60% of an organic solvent (propylene glycol methyl ether acetate);
1% of a silane coupling agent (vinyl trimethoxy silane);
3% of auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Comparative example 2
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a host resin (OSC) 30%;
antifouling filler (disulfide bond compound modified Al) 2 O 3 Hexadecylpolysiloxane modified SiO2 mass ratio = 1:5) 5%;
1% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone);
60% of an organic solvent (propylene glycol methyl ether acetate);
1% of a silane coupling agent (vinyl trimethoxy silane);
auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1 (m/m) 3%).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Comparative example 3
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a main resin (modified acrylic resin, trade name is the courtesy chemical hypomerfs-2820) 30%;
antifouling filler (disulfide bond compound modified Al) 2 O 3 Hexadecylpolysiloxane modified SiO 2 Mass ratio = 1:5) 5%;
1% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone);
60% of an organic solvent (propylene glycol methyl ether acetate);
1% of a silane coupling agent (vinyl trimethoxy silane);
auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1 (m/m) 3%).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Comparative example 4
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a bulk resin (SAC/OSC mass ratio=1:3) 30%;
antifouling filler (disulfide bond compound modified Al) 2 O 3 )5%;
1% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone);
60% of an organic solvent (propylene glycol methyl ether acetate);
1% of a silane coupling agent (vinyl trimethoxy silane);
auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1 (m/m) 3%).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Comparative example 5
The only difference from example 1 is that the anti-fouling coating liquid comprises the following components in mass ratio:
a bulk resin (SAC) 30%;
antifouling filler (disulfide bond compound modified Al) 2 O 3 Hexadecylpolysiloxane modified SiO 2 Mass ratio = 1:5) 5%;
1% of photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone);
60% of an organic solvent (propylene glycol methyl ether acetate);
1% of a silane coupling agent (vinyl trimethoxy silane);
3% of auxiliary agent (polydimethylsiloxane leveling agent/BYK-104S dispersant mass ratio=1:1).
Adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the coating liquid composition.
Experiment one transparent back sheet was prepared using the anti-fouling coating solutions of examples 1 to 8 and comparative examples 1 to 5
The preparation method comprises the following steps:
firstly, carrying out corona treatment on the inner surface of a 275 mu m PET substrate, coating a bonding layer coating liquid (eagle PF 750), drying at 80-180 ℃ in a gradient manner for 1-5min, and curing at room temperature for 24h to obtain the 8 mu m thick bonding coating.
Secondly, carrying out corona treatment on the outer surface of the PET substrate, coating weather-resistant layer coating liquid (eagle PF 750), drying at 80-180 ℃ in a gradient manner for 1-5min, and curing at room temperature for 24h to obtain the 18 mu m-thick weather-resistant coating.
Thirdly, preparing an anti-fouling coating: and (3) coating an anti-fouling coating liquid on the outer surface of the weather-resistant coating, curing the anti-fouling coating for 120s under a UV lamp with the wavelength of 365nm, wherein the dry thickness of the anti-fouling coating is 3 mu m, and thus, the preparation of the coated transparent backboard is completed.
The photovoltaic backsheet prepared above was subjected to the following measurements:
outer coating hydrophobicity: the contact angle of the anti-fouling coating was tested with reference to standard GBT 30693-2014.
Adhesion of the anti-fouling coating: the measurement is carried out according to the cross-cut test method of GB/T928-1998 colored paint and varnish film;
light transmittance of the anti-fouling coating: the anti-fouling coating was tested for total light transmittance (abbreviated as transmittance or light transmittance) according to the standard of JISK7105-1981 test method for optical Properties of plastics.
Sand falling test: the anti-sand dropping property of the outer coating is tested according to the standard of GB/T31034-2014 insulating back plate for crystalline silicon solar cell module.
QUV aging: according to the standard of GB/T31034-2014 insulating backboard for crystalline silicon solar cell module, an ultraviolet aging lamp is used for treatment, the accumulated ultraviolet energy reaches 240 kwh/square meter, and a sample is taken out to observe the appearance yellowing value delta b of the transparent backboard.
And (3) wet heat aging treatment: according to the standard of GB/T31034-2014 insulating backboard for crystalline silicon solar cell module, the temperature and humidity of a high-temperature high-humidity box body are set to be 85 ℃, the humidity is 85%, the accumulation time is 2000 hours, and a sample is taken out to test the hydrophobicity and the light transmittance of the anti-fouling coating.
The results of the above performance tests are shown in table 1 below:
the foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. An anti-fouling coating liquid composition is characterized in that the raw materials of the composition comprise main resin, anti-fouling filler, photoinitiator, organic solvent, silane coupling agent and auxiliary agent; wherein the antifouling filler comprises disulfide bond compound modified Al 2 O 3 And hexadecylpolysiloxane modified SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The disulfide bond-containing compound modified Al 2 O 3 And hexadecylpolysiloxane modified SiO 2 The mass ratio of (2) is 1:5-5:1.
2. The coating liquid composition according to claim 1, wherein the main resin comprises a disulfide bond-containing urethane acrylic resin and a silicone-modified urethane acrylate; the mass ratio of the disulfide bond-containing polyurethane acrylic resin to the organosilicon modified polyurethane acrylic ester is 1:3-3:1.
3. The coating liquid composition according to claim 2, wherein the preparation method of the disulfide bond-containing urethane acrylic resin comprises the steps of mixing an aromatic urethane acrylate oligomer and 4,4' -diaminodiphenyl disulfide, and reacting for 2-4 hours at 70-90 ℃ in a nitrogen atmosphere.
4. The coating liquid composition according to claim 1, wherein the disulfide-containing compound is a compound comprising a disulfideBond compound modified Al 2 O 3 The preparation method comprises reacting 2-hydroxyethyl disulfide with isocyanate methyltrimethoxysilane to obtain disulfide bond-containing siloxane compound, and then reacting Al 2 O 3 Adding the disulfide bond-containing siloxane compound and KH550 hydrolysate into the dispersion liquid, and reacting to obtain the final product.
5. The coating liquid composition according to claim 1, wherein the hexadecylpolysiloxane modified SiO 2 The preparation method of (C) comprises the steps of preparing hexadecyltrimethoxysilane, tetraethoxysilane and SiO 2 The catalyst is obtained through HCl catalytic reaction.
6. The coating liquid composition according to claim 1, wherein the photoinitiator is selected from any one or more of benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, alpha-aminoalkyl phenone, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 9-phenylacridine; the organic solvent is one or more of ethanol, n-butanol, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, xylene and butanone; the silane coupling agent is one or more selected from vinyl trimethoxy silane, vinyl tri (beta-methoxyethoxy) silane, vinyl triisopropoxy silane, vinyl triethoxy silane, gamma-methacryloxypropyl trimethoxy silane and vinyl triacetoxy silane; the auxiliary agent comprises one or two of a leveling agent and a dispersing agent.
7. The coating liquid composition according to claim 1, wherein the raw materials of the composition comprise the following components in percentage by weight:
30% -50% of main resin;
5% -10% of anti-fouling filler;
1% -5% of a photoinitiator;
30% -60% of organic solvent;
1% -5% of a silane coupling agent;
1-8% of auxiliary agent.
8. The coating liquid composition according to any one of claims 1 to 7, wherein the antifouling coating layer has a thickness of 1 to 5 μm.
9. A method for preparing the coating liquid composition according to any one of claims 1 to 8, comprising the steps of: adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and the auxiliary agent into the organic solvent, and uniformly mixing to obtain the anti-fouling adhesive.
10. Use of a coating liquid composition according to any one of claims 1-8 for the preparation of a long-lasting self-cleaning transparent backsheet.
CN202310921663.6A 2023-07-26 2023-07-26 Anti-fouling coating liquid composition, preparation method and application Pending CN116948515A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021819A (en) * 2010-10-22 2011-04-20 东华大学 Fluorine-free superhydrophobic finishing agent containing modified nano silicon dioxide hydrosol and application thereof
CN109233423A (en) * 2018-09-26 2019-01-18 广州市嵩达新材料科技有限公司 A kind of modified Nano particle and preparation method thereof and super-hydrophobic selfreparing photocureable coating prepared therefrom
CN114854243A (en) * 2022-05-20 2022-08-05 义乌市中力工贸有限公司 Preparation method and application of modified silicon dioxide for environment-friendly water-repellent oil-repellent coating
KR20230018729A (en) * 2021-07-30 2023-02-07 주식회사 유니드비티플러스 High hard uv coat composition, high hard uv coating paper using the same, and article using the uv coating paper

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021819A (en) * 2010-10-22 2011-04-20 东华大学 Fluorine-free superhydrophobic finishing agent containing modified nano silicon dioxide hydrosol and application thereof
CN109233423A (en) * 2018-09-26 2019-01-18 广州市嵩达新材料科技有限公司 A kind of modified Nano particle and preparation method thereof and super-hydrophobic selfreparing photocureable coating prepared therefrom
KR20230018729A (en) * 2021-07-30 2023-02-07 주식회사 유니드비티플러스 High hard uv coat composition, high hard uv coating paper using the same, and article using the uv coating paper
CN114854243A (en) * 2022-05-20 2022-08-05 义乌市中力工贸有限公司 Preparation method and application of modified silicon dioxide for environment-friendly water-repellent oil-repellent coating

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